Spin-State Ordering in Hydroxo-Bridged Diiron(III)bisporphyrin Complexes

ABSTRACT We report the synthesis, structure, and spectroscopic characterization of 1,2-bis[μ-hydroxo iron(III) 5-(2,3,7,8,12,13,17,18-octaethylporphyrinyl)]ethane with PF6- and SbF6- counteranions. The two iron centers are nonequivalent with admixed intermediate spin state (S = 3/2 with a minor contribution of S = 5/2) on each metal both in the solid and in solution. The molecules are compared with previously known μ-hydroxo complexes with other counterions, such as I3-, BF4-, and ClO4-, which demonstrates that the nature of the counterion can affect the spin-state ordering dramatically. To understand how the spin-state ordering is affected by external perturbations, we also have done a comprehensive computational study. The calculations show that subtle environmental perturbations affect the spin-state ordering and relative energies and are likely to be the root cause of the variation in spin-state ordering observed experimentally. Spin-State Ordering in Hydroxo-Bridged Diiron(III)bisporphyrin Complexes - ResearchGate. Available from: http://www.researchgate.net/publication/271335102_Spin-State_Ordering_in_Hydroxo-Bridged_Diiron%28III%29bisporphyrin_Complexes [accessed May 14, 2015].